US4101318A - Cemented carbide-steel composites for earthmoving and mining applications - Google Patents

Cemented carbide-steel composites for earthmoving and mining applications Download PDF

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US4101318A
US4101318A US05/749,343 US74934376A US4101318A US 4101318 A US4101318 A US 4101318A US 74934376 A US74934376 A US 74934376A US 4101318 A US4101318 A US 4101318A
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steel
binder
cemented carbide
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Erwin Rudy
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Esco Corp
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Priority to JP11910277A priority patent/JPS5372710A/ja
Priority to FR7734954A priority patent/FR2373500A1/fr
Priority to BR7707794A priority patent/BR7707794A/pt
Priority to GB51037/77A priority patent/GB1597715A/en
Priority to AU31362/77A priority patent/AU504992B2/en
Priority to SE7714037A priority patent/SE7714037L/xx
Priority to DE19772754999 priority patent/DE2754999A1/de
Priority to CA292,776A priority patent/CA1087878A/en
Priority to AT886977A priority patent/AT352641B/de
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C33/00—Making ferrous alloys
    • C22C33/02—Making ferrous alloys by powder metallurgy
    • C22C33/0257—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements
    • C22C33/0278—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements with at least one alloying element having a minimum content above 5%
    • C22C33/0292—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements with at least one alloying element having a minimum content above 5% with more than 5% preformed carbides, nitrides or borides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D19/00—Casting in, on, or around objects which form part of the product
    • B22D19/06—Casting in, on, or around objects which form part of the product for manufacturing or repairing tools
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F7/00—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression
    • B22F7/06—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite workpieces or articles from parts, e.g. to form tipped tools
    • B22F7/08—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite workpieces or articles from parts, e.g. to form tipped tools with one or more parts not made from powder
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/10—Alloys containing non-metals
    • C22C1/1036—Alloys containing non-metals starting from a melt
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
    • C22C29/02—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides
    • C22C29/06—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds
    • C22C29/067—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds comprising a particular metallic binder
    • E—FIXED CONSTRUCTIONS
    • E02—HYDRAULIC ENGINEERING; FOUNDATIONS; SOIL SHIFTING
    • E02F—DREDGING; SOIL-SHIFTING
    • E02F9/00—Component parts of dredgers or soil-shifting machines, not restricted to one of the kinds covered by groups E02F3/00 - E02F7/00
    • E02F9/28—Small metalwork for digging elements, e.g. teeth scraper bits
    • E02F9/2808—Teeth
    • E02F9/285—Teeth characterised by the material used
    • E—FIXED CONSTRUCTIONS
    • E21—EARTH OR ROCK DRILLING; MINING
    • E21C—MINING OR QUARRYING
    • E21C35/00—Details of, or accessories for, machines for slitting or completely freeing the mineral from the seam, not provided for in groups E21C25/00 - E21C33/00, E21C37/00 or E21C39/00
    • E21C35/18—Mining picks; Holders therefor
    • E21C35/183—Mining picks; Holders therefor with inserts or layers of wear-resisting material
    • E—FIXED CONSTRUCTIONS
    • E21—EARTH OR ROCK DRILLING; MINING
    • E21C—MINING OR QUARRYING
    • E21C35/00—Details of, or accessories for, machines for slitting or completely freeing the mineral from the seam, not provided for in groups E21C25/00 - E21C33/00, E21C37/00 or E21C39/00
    • E21C35/18—Mining picks; Holders therefor
    • E21C35/183—Mining picks; Holders therefor with inserts or layers of wear-resisting material
    • E21C35/1833—Multiple inserts
    • E—FIXED CONSTRUCTIONS
    • E21—EARTH OR ROCK DRILLING; MINING
    • E21C—MINING OR QUARRYING
    • E21C35/00—Details of, or accessories for, machines for slitting or completely freeing the mineral from the seam, not provided for in groups E21C25/00 - E21C33/00, E21C37/00 or E21C39/00
    • E21C35/18—Mining picks; Holders therefor
    • E21C35/183—Mining picks; Holders therefor with inserts or layers of wear-resisting material
    • E21C35/1835—Chemical composition or specific material
    • E—FIXED CONSTRUCTIONS
    • E21—EARTH OR ROCK DRILLING; MINING
    • E21C—MINING OR QUARRYING
    • E21C35/00—Details of, or accessories for, machines for slitting or completely freeing the mineral from the seam, not provided for in groups E21C25/00 - E21C33/00, E21C37/00 or E21C39/00
    • E21C35/18—Mining picks; Holders therefor
    • E21C35/183—Mining picks; Holders therefor with inserts or layers of wear-resisting material
    • E21C35/1837—Mining picks; Holders therefor with inserts or layers of wear-resisting material characterised by the shape
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F5/00—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product
    • B22F2005/001—Cutting tools, earth boring or grinding tool other than table ware
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C2204/00—End product comprising different layers, coatings or parts of cermet
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12535—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.] with additional, spatially distinct nonmetal component
    • Y10T428/12576—Boride, carbide or nitride component

Definitions

  • the present invention relates to composites comprising a heat treatable tungsten carbide-based cemented carbide component and a heat treatable steel component which are particularly useful for earthmoving and mining applications.
  • the composites of the invention are fabricated by integral casting of the cemented carbide in steel.
  • Typical modern earthmoving equipment has replaceable wear tips, also referred to as digger teeth, on the ground-engaging part of the machinery.
  • the digger teeth are subjected to abrasive wear as movement of the tool forces ground material to flow under varying pressure along the surfaces of the wear tips.
  • the tips may also be exposed to high mechanical shock loads if digging is performed in ground with gross inhomogenization with respect to size and consistencies of the constituent, such as the presence of large rocks in ordinary soil.
  • Useful wear life of the digger teeth depends on many factors, and may extend from several hundred hours down to minutes in cases where a combination of hard and highly abrasive material and high operating temperatures cause rapid attrition of the wear tip by macroscopic chip removal of the ground-engaging surfaces.
  • the high cost of such operations has promoted extensive work to improve, by many different means, the productive wear life of the wear tips.
  • hard facing One widely used means for improving the wear life of earthmoving and mining tools by use of carbides is hard facing.
  • a wear resistant layer typically consisting of dispersions of chromium carbides or tungsten carbides in ferrous metal alloys are applied to the steel surface of consumable electrode welding.
  • the carbide-containing facings are, however, quite brittle and have a tendency to spall when subjected to sudden mechanical loads.
  • Other commonly used hard facings on steel include dispersions of grains of cast WC + W 2 C eutectic, or crushed WC-Co cemented carbide alloys, in low melting alloy matrices, such as manganese bronze. The low hardness of these matrix alloys prevents their use in applications other than in purely abrasive conditions.
  • a disadvantage common to all hard facings results from the fact that heat applied during the application decreases the hardness, and thus strength and wear resistance of the steel substrate and the thermo-mechanical and metallurgical properties of the hardfacing generally precludes heat treatment of the composite wear tip following the hardfacing operation.
  • the brittleness and thermal shock sensitivity coupled with the low melting temperatures of the brazing alloy and the large thermal expansion difference between carbide and steel, prevents a hardening of the steel component in the composite tool, thus necessitating careful design of the tool geometry to prevent excessive wear of the steel support.
  • a heat treatable composite structure comprising a heat treatable cemented carbide component and a heat treatable steel component.
  • the cemented carbide component comprises a sintered component including grains of monocarbide based substantially on the hexagonal solid solution (Mo,W)C embedded in a binder of heat treatable steel alloy, with the binder being from 30 to 80 percent by volume of the cemented carbide component.
  • the steel component of the treatable composite structure is formed from a castable low alloy steel.
  • the preformed cemented carbide component is joined to the steel component by placing the cemented carbide component having the desired geometry in a selected location of a casting mold, and pouring molten steel into the mold assembly so as to form, after solidification, a composite in which the cemented carbide component is integrally bonded to the steel component by diffusion bonding and is prestressed into compression as the steel component solidifies around the cemented carbide component.
  • the cemented carbide-steel composite is then heat treated according to the practices employed for the steel component for the purpose of attaining the desired hardness and toughness properties, and the heat treated component is used as a wear component in a earthmoving or mining tool.
  • the cemented carbide the amount and geometry of which is selected according to their requirements of a specific application, serves the express purpose of prolonging the wear life of the steel components.
  • a composition of material which comprises sintered carbide-binder metal alloys which has the desired hardness and toughness properties for use in earthmoving or mining tools and which has the ability to withstand the thermal shock of being integrally cast into the steel component and which can further stand heat treatment according to the practices employed in the industry to impart the desired characteristics to the steel component to which the carbide component is integrally bound.
  • the composition of material comprises sintered carbide-binder metal alloys in which the carbide comprises grains of monocarbide based substantially on the hexagonal solid solution (Mo,W)C embedded in a binder of heat treatable steel alloy which contains between 0.40 and 8.0 percent by weight chromium, between 0.40 and 8.0 percent by weight of a metal selected from the group consisting of molybdenum and tungsten, less 1.5 percent by weight vanadium and between 0.15 and 1.20 percent by weight carbon, with the binder metal being from 40 to 80 percent by volume of the compositon of material.
  • the carbide comprises grains of monocarbide based substantially on the hexagonal solid solution (Mo,W)C embedded in a binder of heat treatable steel alloy which contains between 0.40 and 8.0 percent by weight chromium, between 0.40 and 8.0 percent by weight of a metal selected from the group consisting of molybdenum and tungsten, less 1.5 percent by weight vanadium and between 0.15 and 1.20 percent by weight carbon, with the binder
  • a method of making the above-described composition of material which allows the material to be sintered to substantially full density while avoiding the formation of undesirable ⁇ -carbides.
  • a powder mixture of binder and carbides having the desired gross composition is first prepared in which the binder portion of the powder mixture comprises iron powder whose average diameter is less than 40 micrometers alloyed with up to 10 weight percent other iron group elements (nickel and cobalt) and not more than 0.2 weight percent vanadium and 1.5 weight percent chromium.
  • any additional chromium and vanadium desired in the binder portion of the mixture is added to the powder mixture as carbides, and the molybdenum and tungsten components of the binder mixture are added as either elemental powders or carbides.
  • the powder mixture is then wet milled to increase the sintering activity of the iron powder, and is then dried and homogenized.
  • the powder mixture is then pressed into compacts having the desired shape and is then sintered to substantially full density at sintering temperatures not higher than the temperature at which ⁇ -carbides are formed for the particular solid solution (Mo,W)C.
  • FIG. 1 is a graph showing the lower temperature limits for ⁇ -carbide formation in steel-bonded tungsten -- molybdenum monocarbide alloy as a function of the MoC content in the carbide and at different chromium levels in the binder, and also shows the practical minimum sintering temperature for complete densification.
  • FIGS. 2a and 2b are microstructures of a steel-bonded tungsten carbide sintered at 1295° C (2a) and 1255" C (2b), the sintered alloy having the gross composition 0.68 moles (Fe.sub..95 Cr.sub..025 Mo.sub..025)C.sub..029 and .32 moles of WC.
  • FIG. 2a shows the formation of large islands of brittle M 6-12 C ( ⁇ -carbide) phase at a magnification of 1000 when the chosen sintering temperature is too high, while the micrograph in FIG. 2b reveals only WC at the correct sintering temperature of 1255° C.
  • FIG. 3 is a graphical presentation of the transverse rupture strengths of steel-bonded group VI metal carbide alloys as a function of the sintering temperature.
  • the samples referred to in FIG. 3 were heat treated by oil quenching from 1050° C followed by a one-hour temper at 500° C and had the following gross composition:
  • Sample A .31 moles (Mo.sub..5 W.sub..5)C and .69 moles (Fe.sub..93 Cr.sub..025 Mo.sub..025 Ni.sub..02)C.sub..0292
  • Sample B .31 moles WC and .69 moles (Fe.sub..93 Cr.sub..025 Mo.sub..025 Ni.sub..02)C.sub..0292
  • Sample C .31 moles WC and .69 moles (Fe.sub..89 Cr.sub..025 Mo.sub..025 Co.sub..05 Ni.sub..01)C.sub..0292
  • FIG. 4 is a graphical presentation of the transverse rupture strengths of a steel-bonded tungsten carbide alloy as a function of the tempering temperature, the carbide having a gross composition of 0.33 moles WC and 0.67 moles (Fe.sub..95 Cr.sub..032 Mo.sub..018)C.sub..0215.
  • FIG. 5 is a graphical presentation of the Rockwell C hardness of a steel-bonded tungsten carbide alloy as a function of the quenching temperature and tempering treatment, the carbide having a gross composition .33 moles WC and .67 moles (Fe.sub..94 Cr.sub..025 Mo.sub..025)C.sub..030.
  • FIG. 6 is a graphical presentation of the transverse rupture strengths of a steel-bonded tungsten carbide as a function of the carbide content.
  • FIG. 7 is a graphical presentation of the relative wear resistance against an Al 2 O 3 abrasive of commercial WC-Co cemented tungsten carbides and of steel-bonded tungsten carbide as a function of the binder content.
  • FIG. 8 is a micrograph of the interface of steel-bonded tungsten carbide integrally cast into low alloy steel in the fully heat treated and tempered condition of a magnification of 400.
  • Zone A in FIG. 8 is a low alloy steel with 2% nickel and .25% carbide and has a Rockwell C hardness of 50.
  • Zone B in FIG. 8 is the interdiffusion zone between steel and the steel-bonded carbide with a measured Rockwell C hardness of 69.
  • FIG. 9 is a micrograph of the steel/cemented carbide interface of a steel-bonded tungsten carbide integrally cast into steel and depicts the formation of Ledeburite eutectic at excessive casting temperatures.
  • the magnification of the micrograph depicted in FIG. 9 is 160 times; Zone A shows the unaffected low alloy steel; Zone B, primary steel grains surrounded by Ledeburite eutectic; Zone C, the interdiffusion zone steel/cemented carbide; and Zone D, the unaffected cemented carbide.
  • FIG. 10 is a micrograph of a magnification of 600 times showing the interface between steel-bonded tungsten carbide and low alloy steel of a composite formed by resistance welding.
  • the light area of the micrograph of FIG. 10 shows the cemented carbide and the dark area the low alloy steel in heavily etched condition.
  • FIG. 11 is a micrograph of the steel/cemented carbide interface of a steel-bonded tungsten carbide which has been coated with a brazing alloy prior to integral casting in steel at a magnification of 500.
  • Zone A in FIG. 11 depicts the cast steel
  • Zone B the layer of high temperature brazing alloy with an average layer thickness of 100 micrometers and a gross composition 65 weight percent Cu, 30 weight percent Ni and 5 weight percent Mn
  • Zone C the steel-bonded tungsten carbide.
  • FIGS. 12a and 12b are micrographs of different magnifications of the steel/cemented carbide interface of a steel-bonded tungsten carbide which has been coated with a 1000 micrometer surface layer of high temperature brazing alloy prior to integral casting in steel.
  • FIG. 12a depicts, at a magnification of 25, in Zone A the cast steel, in Zone B the layer of high temperature brazing alloy with a gross composition 78 weight percent Cu, 20 weight percent Ni, 2 weight percent Mn, and in Zone C the steel-bonded carbide.
  • FIG. 12b depicts at a magnification of 600 times the microstructure at the cemented carbide/brazing alloy interface of the composite shown in FIG. 12a.
  • FIG. 13 is illustrations of preferred carbide coverages of steel digger teeth operating at high (> 70°) positive angles of attack in earthmoving applications.
  • the integrally cast carbide inserts are shown cross-hatched.
  • FIG. 14 is illustrations of preferred carbide coverages of steel digger teeth operating at angles of attack of less than +35 degrees.
  • the integrally cast carbide inserts are shown cross-hatched.
  • FIG. 15 is illustrations of integrally cast carbides in mining tools.
  • the configurations denoted A and B in FIG. 15 are typical tools used in augers and coal miners, while C illustrates a section of a tricone drilling bit.
  • x, x', x" . . . are, respectively, the relative mole fractions (metal exchanges) of the metal constituents M, M', M" . . . It is noted that 100x defines mole percent MC z or mole percent MC z -exchange, 100.x" mole percent M"C z or mole percent M"C z exchange, etc.
  • This method of defining the overall composition is particularly useful in describing the concentration spaces of interstitial alloys and will be used, sometimes in conjunction with compositions given in weight percent of the individual component, throughout the remainder of this specification.
  • the carbon balance of the binder, in conjunction with the other alloying elements present in the binder, also has a significant effect on alloy properties and sintering behavior, and has to be kept within certain defined limits in order to obtain the best compromise between fabricability, binder heat treatability and toughness, stability of the carbide phase.
  • Tungsten monocarbide forms a stable solid state equilibrium with iron, whereby an increasing amount of tungsten carbide is dissolved in the iron with increasing temperature. Owing to the high solubility of carbon in the austenitic steel, no free carbon is formed along the join WC + Fe, as the vertex of the three-phase equilibrium
  • phase equilibrium the same sequence of phase equilibria should be traversed in reverse when the temperature is lowered, but in practice this is not found because the ⁇ -carbide, once formed, dissolved only extremely slowly and reestablishment of the true equilibrium condition at low temperatures generally is not possible within feasible length of time. In practice, therefore, the equilibrium
  • the incipient melting temperatures of the alloy drop and approach the melting temperatures of the binery Fe-C eutectic.
  • the relative proportion of WC retained in the alloy exposed to a given temperature above incipient melting will be larger because tungsten monocarbide, rather than the ⁇ -carbide, becomes the primary crystallizing phase.
  • the last product of crystallization in such alloys is Ledeburite eutectic, which generally form a fine-grained network of cementite and other carbides around the iron-rich metal grains, and causing the alloys to become very brittle.
  • the cementite lattice at the grain boundaries cannot be removed by prolonged solutioning or normalizing treatments at subsolidus temperatures.
  • Molybdenum monocarbide, MoC when alloyed with WC, causes a decrease in the stability of WC, but also lowers the incipient melting of the cemented carbides and therefore temperatures necessary to achieve densification.
  • the upper practical limit for MoC is approximately 50 mole percent, as at higher molybdenum carbide concentrations even the minimum chromium content of 0.4 weight percent in the steel binder considered necessary for adequate hardenability, will result in the formation of detrimental quantities of ⁇ -carbide at 1150° C, which was found to be the lowest temperature at which complete densification could be achieved.
  • the element chromium has a pronounced destabilization effect on the hexagonal monocarbide, and a moderate destabilization effect on the ⁇ -carbide.
  • concentration levels of chromium in the binder phase which be between 1.8 and 4.5 percent based on the weight of the binder, no significant formation of ⁇ - and M 2 C carbide is observed when the carbide is WC, and even at 6.5 weight percent chromium in the binder only insignificant quantities of M 2 C and ⁇ -carbide are found if the sintering temperatures are kept below 1260° C.
  • chromium in the binder are progressively reduced upon increased substitution of tungsten carbide by molybdenum carbide.
  • a powder mixture according to the desired gross composition is prepared from the ingredient powders consisting of tungsten monocarbide, or (Mo,W)C, iron, chromium carbide, molybdenum and tungsten and, if necessary for establishing the proper carbon stoichiometry Mo 2 C and W 2 C.
  • the initial mixture contains only about one-half of the required amount of iron to facilitate homogenization and comminution of selected addition metal carbides, in particular Cr 3 C 2 .
  • the initial powder mixture is wetmilled under an inert fluid such as naptha for about one-third of the total milling time, the balance of the iron powder added after the premilling period, and wetmilling continued for the remaining two-thirds of the milling cycle.
  • This wetmilling is necessary to increase the sintering activity of the iron powder.
  • Typical total milling times are between 48 to 85 hours in a ball mill, and between 8 and 14 hours in an agitated attritor mill.
  • a pressing aid such as paraffine is added to the powder slurry in the mill towards the end of the milling cycle.
  • the milled powder slurry is discharged from the mill, dried and homogenized to achieved uniform distribution of the pressing aid.
  • the powder is then precompacted and granulated to yield ready-to-press grade powder for fabrication of the cemented carbide.
  • the grade powder is compacted into parts of the desired shape at pressures varying from 0.5 to 2 tons per square centimeter, the compacts dewaxed under vacuum or hydrogen, and the dewaxed parts sintered to full density at temperatures less than 1285° C, but typically at 1255" for cemented WC, and 1150° C for cemented (W.sub..5 Mo.sub..5)C. Sintering temperature as a function of the MoC exchange is shown in FIG. 1.
  • the sintered compacts are then annealed using the annealing schedule for steels with similar composition as the binder phase in the cemented carbides.
  • the iron In the batching of the gross composition, the iron must be unalloyed powder with a preferred average grain size from 5 to 8 micrometers, but not exceeding 40 l micrometers.
  • the only metallic impurities which may be present in alloyed form in appreciable quantities in the ingredient iron powder are cobalt and nickel.
  • the presence of quantities of more than 0.2 weight percent vanadium and more than 1.5 weight percent chromium in alloyed form in the iron tends to result in porosity of the sintered parts as a result of surface oxide not reduced by action of carbon or hydrogen at presintering temperatures. Elemental chromium has very poor milling characteristics and always present surface oxides can cause severe porosity problems in the sintered alloys.
  • chromium into the binder phase should therefore always be in the form of preformed charbides, such as Cr 3 C 2 .
  • Molybdenum, and tungsten, as well as molybdenum or tungsten carbides such as Mo 2 C and W 2 C, can be added without detriment to the sintering behavior.
  • binder or carbide alloying with vanadium or vanadium carbide is not recommended for any of the compositions of the invention, although concentrations in amounts in the order of 1 percent by weight of the binder may be tolerated. Similarly, no beneficial effects are realized by additions of such other carbides such as TiC, HfC, NbC, and TaC.
  • the chief carbide ingredient in the cemented carbide is tungsten carbide, which may contain up to a maximum of 50 mole percent, but preferably not more than 25 mole percent, molybdenum carbide in solid solution.
  • the principal alloying elements in the binder phase are cobalt, nickel, chromium, molybdenum, tungsten, and carbon, other alloying additions being either inert or having an adverse effect on properties and performance.
  • Tables 1 and 2 list some of the gross compositions of steel binders and carbide alloys used in the batching of cemented carbide alloys and the following examples 1 through 4 are representative of the cemented carbide alloy components and the methods used in the fabrication of the composites of the invention. Representative microstructures and properties of the cemented carbide component of the composites of the invention are depicted in FIGS. 2 through 12.
  • a powder mixture consisting of 55.9 weight percent tungsten carbide, 1.158 weight percent chromium carbide, Cr 3 C 2 , 1.967 weight percent Mo 2 C, .621 weight percent nickel and one-half of the amount of the balance of 4.354 weight percent iron are charged into a ball mill containing tungsten carbide balls as grinding media and naphta as milling fluid. After premilling for 20 hours, the remaining half of the iron powder is added and milling continued for an additional 60 hours to achieve the desired degree of comminution and homogenization of the powder mixture. Approximately one hour prior to mill shutdown, approximately 2.2 percent paraffine by weight of the dry powder mass is added to the powder slurry.
  • the milled powder slurry is then separated from the grinding media, dried and homogenized in a high speed mechanical blender.
  • the dry powder mass is then precompacted at a pressure of approximately 0.2 tons per square centimeter and granulated to yield agglomerated grains within a size range from 250 to 1000 micrometers.
  • the granulated powder is pressed at a pressure of 1.5 tons per square centimeter into parts and dewaxed in a 3 hour cycle at 350° C under vacuum.
  • the dewaxed compacts are presintered for approximately 1 hour at 1050° to 1150° C and sintered for 1 hour and 30 minutes at 1258° C under vacuum or hydrogen.
  • the temperature of the furnace is lowered to 1000° C within a 30 minute period and the furnace then cooled at a rate of 15° C per minute until a temperature of 600° C is reached, after which the furnace is shut down.
  • Micrographic examination of the sintered alloy showed grains of tungsten monocarbide uniformly dispersed in a pearlitic steel matrix and the cemented carbide alloy had a Rockwell C hardness of 53.
  • R c Rockwell C
  • Austenitization at 1150° C resulted in an as-quenched hardness of R c 70 and a maximum hardness of R c 72 following a double temper of 1 hour each at 550° C.
  • the values for the transverse rupture strengths given for a similar alloy in the graph of FIG. 3 are also representative for this composition.
  • a powder mixture consisting of 62.74 weight percent WC, 1.76 weight percent Cr 3 C 2 , 1.56 weight percent Mo, 1.92 weight percent Co, 0.58 weight percent Ni, and 31.44 weight percent iron are processed in the same manner as described under Example 1 and the powder compacts sintered for 1 hour and 30 minutes at 1268° C under vacuum.
  • Gross Composition 0.33 moles (Mo.sub..5 W.sub..5 C+.67 moles (Fe.sub..95 Cr.sub..0323 Mo.sub..0177)C.sub..0215
  • a powder mixture consisting of 56.89 weight percent of the prealloyed carbide (Mo.sub..5 W.sub..5)C, 1.47 weight percent Cr 3 C 2 , 1.30 weight percent molybdenum, and 40.34 weight percent iron are processed in the same manner as described under Example 1, sintered for 1 hour at 1155° C, and annealed under the same conditions as described under Example 2.
  • the hardness of the process-annealed alloy was R c 56.
  • Austenitizing of the cemented carbide for 1 hour at 1100° C, followed by quenching in oil and a doubletemper of 2 hours each at 550° C yielded a hardness of R c 74.5 and a transverse rupture strength of 285 ksi.
  • a melt of 4340 steel (0.40 weight percent C), .85 weight percent Si, .75 weight percent Cr, 1.80 weight percent Ni, .25 weight percent Mo, balance Fe) was prepared by induction melting in a ceramic crucible and poured at a temperature of 1550° C into a ceramic mold containing a process-annealed piece of the cemented carbide described under Example 1.
  • the weight ratio of steel to carbide in the cast piece was 6:1.
  • the steel component had a hardness of R c 48 and the cemented carbide component R c 68.6.
  • the composite structure was then sectioned and shaped into a transverse rupture test sample.
  • the measured rupture strength of the cemented carbide/4340 steel interface was 162 ksi.
  • measured loss ratios of the same cemented carbide integrally cast into a digger tooth under actual service conditions in abrasive soil varied between 55 to 85.
  • compositions of castable low alloy steels are from 0.3 to 3 weight percent chromium, 0.2 to 3 weight percent molybdenum and/or tungsten, 0 to 4 percent manganese, with the nickel and manganese combined being up to 5 weight percent, and from 0.15 to 0.80 weight percent carbon, but typically 0.25 weight percent carbon.
  • Chromium in amounts up to 3 percent by weight of the binder improve hardenability of the cemented carbide, while higher concentrations caused a slight decrease in toughness without commensurate improvement in the heat treatment characteristics. Variations in the chromium content within the preferred concentration range of 1.8 percent to 4.5 percent did not have a noticeable effect on the interface bonding characteristics of the integrally cast parts.
  • Molybdenum in amounts up to 4.5 percent in the binder phase have a more pronounced effect on hardenability than the equivalent amount of tungsten, although the attainable strength levels are about equivalent.
  • molybdenum generally lowers the incipient melting temperatures of the cemented carbides, while they are raised by tungsten.
  • Molybdenum-bearing alloys therefore generally require lower steel pouring temperatures than cemented carbides equivalently alloyed with tungsten.
  • cobalt additions in amounts of up to 8 percent by weight of the binder improves hot hardness of the composite at a slight decrease in fracture toughness and transverse rupture strength.
  • Cobalt, and to a somewhat lesser degree, also nickel increases the temperature at which the carbide loses its shape as a result of melting, and thus lessens the control requirements for pouring temperatures in forming the integrally cast part.
  • the optimum range of carbon stoichiometry of the binder phase is dependent on the amount and nature of its constituents. If the binder composition is characterized by
  • M iron group metals Fe, Co, Ni
  • M' elements forming stable carbides such as Mo, W, Cr
  • the ratio z/y should gall into the range from 0.45 to 1.20, but preferably between 0.50 and 0.75.
  • High carbon contents of the binder (z/y > 0.90) at high levels of alloying additions, in particular of chromium and molybdenum (y > .10) adversely affects integral castability of the cemented carbide due to the high proportion of liquid phase formed at temperatures slightly above incipient melting.
  • the concentration of carbide in the cemented carbide alloy has a pronounced effect on integral castability inasmuch as the differential of the thermal expansion between the cemented carbide and the steel component increases with increased carbide loading, and the thoughness of the carbide also decreases.
  • the maximum size of the cemented carbide parts of a given concentration which can be integrally cast in steel without delamination during heat treatment progressively decreases. Foundry experience and filed tests, have shown the most useful range to extend from about 35 volume percent to 60 volume percent monocarbide in the sintered alloy.
  • brazing material having a thickness of from 50 to 250 micrometers between the carbide component and the steel component. Since the stresses during operation tend to drive the carbide into the steel rather than to attempt to tear the carbide from the steel, the direct diffusion bonding between the sintered carbide-binder and the steel is less important to provide tensile strength, and the brazing material provides a cushioning layer between the components to help absorb impact energy while the tool is in use.
  • the brazing material is a nickel or copper base alloy with a melting temperature between 1050° C and 1300° C.
  • FIGS. 11 and 12 show micrographs of such structures.

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US05/749,343 1976-12-10 1976-12-10 Cemented carbide-steel composites for earthmoving and mining applications Expired - Lifetime US4101318A (en)

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Application Number Priority Date Filing Date Title
US05/749,343 US4101318A (en) 1976-12-10 1976-12-10 Cemented carbide-steel composites for earthmoving and mining applications
JP11910277A JPS5372710A (en) 1976-12-10 1977-10-05 Production of heat treatable composite structure
FR7734954A FR2373500A1 (fr) 1976-12-10 1977-11-21 Matieres composites a base de carbure fritte pour operations de terrassement et de mine, et leur procede de preparation
BR7707794A BR7707794A (pt) 1976-12-10 1977-11-23 Estrutura composta tratavel termicamente de ligante de carbureto cementado e metal ou aco de baixa liga e processo
GB51037/77A GB1597715A (en) 1976-12-10 1977-12-07 Cemented carbidesteel composites their manufacture and use
AU31362/77A AU504992B2 (en) 1976-12-10 1977-12-08 Tipped tool
SE7714037A SE7714037L (sv) 1976-12-10 1977-12-09 Hardmetall-stal-kompositmaterial
DE19772754999 DE2754999A1 (de) 1976-12-10 1977-12-09 Hartkarbidstahlzusammensetzungen fuer erdbewegungs- und bergbau-anwendungen
CA292,776A CA1087878A (en) 1976-12-10 1977-12-09 Cemented carbide-steel composites for earthmoving and mining applications
AT886977A AT352641B (de) 1976-12-10 1977-12-12 Waermebehandelbarer karbid-stahl-verbundkoerper zur verwendung bei werkzeugen und geraeten fuer erdbewegungen und fuer den bergbau

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WO2004076116A1 (en) * 2003-02-26 2004-09-10 Bradken Resources Pty Ltd A steel member and a method of hard-facing thereof
US20050017111A1 (en) * 2003-06-24 2005-01-27 Hickey Jeffrey T. Tool for impinging material having a cast wear pad
US20070217903A1 (en) * 2006-03-14 2007-09-20 Thamboo Samuel V Enhanced bearing durability rotating member method and apparatus
WO2008096213A1 (en) * 2007-02-07 2008-08-14 Sasol-Lurgi Technology Company (Proprietary) Limited Solids handling equipment
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US20090308102A1 (en) * 2008-06-13 2009-12-17 Glenn Miller Tungsten ring composition
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WO2010136055A1 (en) * 2009-05-29 2010-12-02 Metalogenia S.A. Wear element for earth working machine with enhanced wear resistance
WO2010138757A1 (en) * 2009-05-29 2010-12-02 Varel International, Ind., L.P. Milling cap for a polycrystalline diamond compact cutter
US20100307837A1 (en) * 2009-06-05 2010-12-09 Varel International, Ind., L.P. Casing bit and casing reamer designs
US20100319997A1 (en) * 2009-05-29 2010-12-23 Varel International, Ind., L.P. Whipstock attachment to a fixed cutter drilling or milling bit
US20110209922A1 (en) * 2009-06-05 2011-09-01 Varel International Casing end tool
US8323372B1 (en) * 2000-01-31 2012-12-04 Smith International, Inc. Low coefficient of thermal expansion cermet compositions
US8657036B2 (en) 2009-01-15 2014-02-25 Downhole Products Limited Tubing shoe
US8927107B2 (en) 2011-06-03 2015-01-06 Frederick Goldman, Inc. Multi-coated metallic products and methods of making the same
US8956510B2 (en) 2011-06-03 2015-02-17 Frederick Goldman, Inc. Coated metallic products and methods for making the same
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US4216034A (en) * 1977-07-27 1980-08-05 Sumitomo Electric Industries, Ltd. Process for the production of a hard solid solution
US4300952A (en) * 1978-02-28 1981-11-17 Sandvik Aktiebolag Cemented hard metal
US4257809A (en) * 1979-01-05 1981-03-24 General Electric Company Molybdenum monocarbide-tungsten monocarbide solid solutions
US4650722A (en) * 1980-06-13 1987-03-17 Union Carbide Corporation Hard faced article
US4484644A (en) * 1980-09-02 1984-11-27 Ingersoll-Rand Company Sintered and forged article, and method of forming same
US4454205A (en) * 1981-10-09 1984-06-12 Esco Corporation Method of drill bit manufacture and product
US4584020A (en) * 1982-12-06 1986-04-22 Santrade Limited Wear part with high wear strength
EP0279338A1 (en) * 1987-02-20 1988-08-24 Kennametal Inc. Grader blade with tiered inserts on leading edge
US4954058A (en) * 1988-06-27 1990-09-04 Deere & Company Method for making composite sintered apex seal material
US4956012A (en) * 1988-10-03 1990-09-11 Newcomer Products, Inc. Dispersion alloyed hard metal composites
WO1990011383A1 (en) * 1989-03-23 1990-10-04 Kennametal Inc. Wear-resistant steel castings
US5066546A (en) * 1989-03-23 1991-11-19 Kennametal Inc. Wear-resistant steel castings
US5057147A (en) * 1990-06-15 1991-10-15 Gte Products Corporation Method for preparation of WC-NI grade powder
WO1993003231A1 (en) * 1991-07-30 1993-02-18 Caterpillar Inc. Tooth with hard material applied to selected surfaces
US5423899A (en) * 1993-07-16 1995-06-13 Newcomer Products, Inc. Dispersion alloyed hard metal composites and method for producing same
US5403544A (en) * 1993-12-20 1995-04-04 Caterpillar Inc. Method for forming hard particle wear surfaces
US5427186A (en) * 1993-12-20 1995-06-27 Caterpillar Inc. Method for forming wear surfaces and the resulting part
US5502905A (en) * 1994-04-26 1996-04-02 Caterpillar Inc. Tooth having abrasion resistant material applied thereto
EP0726331A2 (en) * 1995-02-08 1996-08-14 Sandvik Aktiebolag Coated titanium-based carbonitride
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US5865385A (en) * 1997-02-21 1999-02-02 Arnett; Charles R. Comminuting media comprising martensitic/austenitic steel containing retained work-transformable austenite
US6080247A (en) * 1997-02-21 2000-06-27 Gs Technologies Operating Company Comminuting media comprising martensitic/austenitic steel containing retained work-transformable austenite
US6369344B1 (en) * 1997-08-19 2002-04-09 Cutting & Wear Developments, Ltd. Substrate facing method, body and kit
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US6632045B1 (en) * 1998-12-24 2003-10-14 Bernard Mccartney Limited Vehicle wheel tooth
US8956438B2 (en) 2000-01-31 2015-02-17 Smith International, Inc. Low coefficient of thermal expansion cermet compositions
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US7235211B2 (en) * 2000-05-01 2007-06-26 Smith International, Inc. Rotary cone bit with functionally-engineered composite inserts
US20040040750A1 (en) * 2000-05-01 2004-03-04 Smith International, Inc. Rotary cone bit with functionally-engineered composite inserts
US8397841B1 (en) 2000-05-01 2013-03-19 Smith International, Inc. Drill bit with cutting elements having functionally engineered wear surface
US6613999B2 (en) * 2000-11-20 2003-09-02 Union Tool Company Method of joining a sintered hard alloy member to a stainless steel member and method of making a cutting tool therefrom
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US20060177689A1 (en) * 2003-02-26 2006-08-10 Darren Muir Steel member and a method of hard-facing thereof
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US20070217903A1 (en) * 2006-03-14 2007-09-20 Thamboo Samuel V Enhanced bearing durability rotating member method and apparatus
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US20090148336A1 (en) * 2007-11-09 2009-06-11 Sandvik Intellectual Property Ab Cast-in cemented carbide components
US20090308102A1 (en) * 2008-06-13 2009-12-17 Glenn Miller Tungsten ring composition
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Also Published As

Publication number Publication date
FR2373500A1 (fr) 1978-07-07
AT352641B (de) 1979-09-25
AU3136277A (en) 1979-06-14
DE2754999C2 (ja) 1987-02-19
GB1597715A (en) 1981-09-09
JPS5372710A (en) 1978-06-28
SE7714037L (sv) 1978-06-11
BR7707794A (pt) 1978-09-12
AU504992B2 (en) 1979-11-01
DE2754999A1 (de) 1978-08-10
FR2373500B1 (ja) 1983-11-25
CA1087878A (en) 1980-10-21
ATA886977A (de) 1979-02-15

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